Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch

Definitions

• the present invention relates to bituminous compositions modified with new polyolefinic materials and particularly suitable for applications either of road surfacing type or building waterproofing.
• bitumens employed for these applications are modified by mixing with modifying materials in order to suitably improve the properties.
• bitumens are easily processable and show good impermeability, but their resistance to ageing is poor and their elastic characteristics are inadequate.
• materials suitable for modifying bitumens must be able to increase the softening temperature and the resistance to elastic failure at high temperatures without negatively affecting the properties at low temperatures and the processability.
• the modifying materials must show a good compatibility degree with bitumen, in order to avoid or at least to limit the arising of segregation phenomena between the bitumen phase and the modifying phase, phenomena which could cause a premature worsening of the properties of the material. It has to be kept in mind with regard to this that the compatibility degree modifier-bitumen is not easily foreseeable because of the complex structure and chemical composition of the bitumen and for the variability depending on the starting crude material and production process.
• modifiers for bitumen are for example homopolymer or copolymer atactic polypropylenes (A-PP), ethylene-propylene rubber (EPR) or ethylene-propylene-ethylidenenorbornene rubber (EPDM), ethylene-vinylacetate copolymer (EVA) or ethylene m-ethylmethacrylate copolymer (EMA) and styrene copolymers such as styrene-butadiene-styrene (SBS) or styrene-isoprene-styrene (SIS).
• A-PP ethylene-propylene rubber
• EPDM ethylene-propylene-ethylidenenorbornene rubber
• EVA ethylene-vinylacetate copolymer
• EMA ethylene m-ethylmethacrylate copolymer
• SBS styrene-butadiene-styrene
• SIS st
• atactic polypropylenes generally show good blendability with bitumens and improve the properties of these at low temperatures, with a slight increase of the elastic recovery, but they contribute little to increase the softening temperature and the penetration.
• EVA and EMA copolymers show a good blendability with bitumens and contribute to increase the softening and properties at the penetration, with fair elastic recovery and properties at the low temperatures.
• EPR or EPDM rubbers in many cases causes insufficiently high softening temperatures and furthermore show blending difficulties with bitumens because of their high viscosity.
• SBS and SIS styrene copolymers give the bitumen elasticity at the low temperatures, but they yield bituminous compositions that are not very resistant to penetration at temperatures higher than 50-60°C; the resistance to ageing is also limited because of the vulnerability of the unsaturated groups to the degrading action of light and atmospheric agents as well as cross-linking phenomena of the product itself.
• EP-A-204157 describes modifiers which comprise an ethylene-propylene elastomeric copolymer and optionally A-PP and/or polyethylene and/or isotactic polypropylene and/or EVA.
• Mixtures of modifiers described in USP 4,829,109 comprise on the contrary an ethylene-propylene copolymer, an ethylene-propylene-diene terpolymer, a high density polyethylene and, optionally, an EVA copolymer.
• bituminous compositions which are particularly suitable for applications either of road surfacing type or building waterproofing using new ethylene copolymers as modifiers.
• the bituminous compositions obtained are particularly interesting in that they combine good elastic properties, resistance to penetration and softening together with an effective resistance to ageing.
• the values of the melting enthalpy indicated under ii. correspond to a restricted crystallinity degree.
• the characteristic described under iv. indicates a random distribution of the ethylene and propylene units and/or of the units deriving from alpha-olefins in sections of the chain having copolymeric structure.
• the combination of characteristics from i. to v. gives the copolymers of the invention valuable elasto-plastic properties; in particular, it is possible to reach a tensile strength higher than 3-4 MPa and tension set values (200%, 1 min., 25°C) lower than 30% on the non vulcanized product.
• Copolymers of the invention generally contain between 35 and 85% by mole of ethylene, between 15 and 65% by mole of propylene and/or alpha-olefins, and between 0 and 10% by mole of units deriving from dienes or polyenes.
• the ethylene content is comprised between 45 and 75% by mole and the propylene and/or alpha-olefins content is comprised between 25 and 55% by mole.
• the content of units from diene or polyene is generally comprised between 0 and 10% by mole, preferably between 0.5 and 2% by mole.
• the copolymers have an intrinsic viscosity comprised between 1.5 and 3.5 inclusive, more preferably between 1.5 and 2.5 inclusive.
• chiral catalysts obtained from metallocene derivatives of zirconium such as ethylene-bis(tetrahydroindenyl)zirconium, dichloride or dimethylsilanylene-bis-(tetrahydroindenyl)zirconium dichloride, and tetraisobutyl-alumoxane.
• the preparation of the copolymers is carried out by copolymerization of mixtures of monomers, working in liquid phase consisting of propylene and/or alpha-olefin at a temperature comprised between about 40 and 50°C.
• Suitable dienes or polyenes are preferably selected from linear non-conjugated diolefins, such as 1,4-hexadiene, or bridged cyclic diolefins such as 5-ethylidene-2-norbornene.
• bitumens used in the compositions of the invention are meant, as described in Kirk-Othmer, "Encyclopedia of Chemical Technology", 3rd Edition, Vol 3, page 84, the two first paragraphs.
• bitumens are those from direct distillation (also called “Straight Run”, SR bitumens) and those deriving from visbreaking (see C. Giavarini, P. De Filippis and F. Del Manso, Intnl. Symposium Chemistry of bitumens, Roma, 1991, vol I, page 314).
• bituminous compositions of the invention can be carried out according to the known blending techniques for the mixing of bitumens with polymeric modifiers.
• the modifiers are mixed in the preheated bitumen, at temperatures higher than the melting point of the components of the mixture.
• a more or less high shear mixing apparatus are used in such a way to obtain an effective dispersion of the modifiers in the bitumen. It is possible, for example, to use a Silverson L4R mixer, according to the process described in the Examples.
• the mixing can also be carried out in two steps, by first preparing a bitumen / modifier masterbatch having a low content of bitumen and thereafter mixing the masterbatch in the remaining part of the preheated bitumen, according to what is described in EP-A-321189.
• bituminous composition of the present invention are particularly suitable either for road surfacing or for building waterproofing , and generally for waterproofing coating of wide surfaces.
• the composition can be used for example as materials for roofs in the "roofing industry" field and in the preparation of waterproof blankets.
• the modification of bitumens according to the invention is in fact effective in improving their elastic behaviour, the resistance to penetration and the softening temperature and allows in an established way the range of characteristics more suitable for the single applications to be obtained.
• a further advantage consists in the good dispersibility / compatibility of the ethylene copolymers of the invention with the bitumen, which allows the performances to be maintained for long periods of time and therefore an effective resistance to ageing.
• the type and the amount of copolymer to be used as modifier in the bituminous compositions of the invention is selected, according to standards known to those skilled in the art, as a function of the requested performance for the application field in which the compositions are used.
• the selection of the type and amount of modifier must also take into account the particular environment conditions (for example the highest and lowest temperature) under which the bituminous compositions of the invention are used.
• the copolymer is used between 3 and 9% by weight of the total, whereas for waterproof blankets the percentages vary between 3 and 20% by weight. Amounts of copolymer out of the indicated ranges can be used without falling out of the meaning of the present invention.
• bituminous compositions of the invention in order to further improve their properties.
• suitable amounts of an isotactic polypropylene can be of use to further increase the softening temperature and the resistance to deformation of the material.
• the content of the bound ethylene is determined by Infrared Analysis.
• the solubility in pentane (characteristic i.) is determined by the following method: 2 g of polymer are placed in 250 ml of pentane; this is heated to boiling under stirring for 20 minutes and thereafter is allowed to cool to 25°C under stirring.
• the melting enthalpy to which is referred under ii. is that measured during the first heating scanning.
• the content of propylene or alpha-olefin units in form of triads is determined by 13 C-NMR with reference to the methine T ⁇ , as reported in "G.J. Ray, P.E. Johnson, J.R. Knox, Macromolecules, 10 , 4, 773 (1977)". Percentage values indicated under iii, are referred to the total propylene or alpha-olefin content.
• the intrinsic viscosity is determined according to ASTM D-2587 at 135°C and in tetrahydronaphthalene.
• Tetraisobutylalumoxane (TIBAO) has been prepared according to Example 2 reported in EP-A-384171.
• Ethylene-bis(tetrahydroindenyl)zirconium dichloride (EBTHIZrCl 2 ) has been prepared following the method described in "H.H. Brintzinger et al., J. Organomet. Chem., 288, page 63, (1985)".
• Toluene has been added to a weighed amount of EBTHIZrCl 2 at the rate of 2 ml for each metallocene mg.
• a toluene solution of TIBAO has been added in such an amount to obtain the molar ratio Al/Zr and the Al molar concentration reported in Table 1.
• the solution has been kept under stirring at the temperature and for the time periods reported in Table 1.
• a 4 litre steel autoclave provided with stirrer, manometer, temperature indicator, feeding system for the catalysts, feeding lines for monomers and thermostating jacket has been used.
• the polymerization has been carried out at 50°C keeping the total pressure constant by feeding ethylene.
• the polymerization conditions have been reported in Table 2.
• the polymer has been dried under vacuum.
• bitumen composition has been characterized, not only by the content of asphaltenes, but also measuring the percentage of aromatic carbon (C ar ) and aromatic hydrogen (H ar ) by NMR analysis.
• ASTM D-133 As to the ductility tests the method ASTM D-133 has been modified. Tests have been carried out at 10°C, by subjecting the specimen to a 20 cm elongation, cutting it in the middle and measuring the dimensional recovery after 1 hour (see F. Van Der Berg, 3rd Eurobitume, The Hague, Vol. I, page 664 (1985)).
• Specimens of mixtures bitumen-modifier employed for the stability test have been prepared by filling an aluminium tube (height 12 cm, diameter 2 cm) with the bituminous composition, keeping the filled tube vertical for 5 days at 140°C, and then cutting the tube in an upper and in a lower part.
• the stability test has been carried out by a penetration test on each of the two parts.
• Bitumen-modifier compositions containing 6% by weight of modifier, calculated on the total weight, have been prepared using a Silverson L4R mixer provided with homogenizing head and operating at 4000 revolutions per minute.
• the mixing of bitumen with the modifier has been carried out by introducing the homogenising head into the bitumen (500 g) preheated at 160°C and inserted into a heating cowling thermostated at 180°C. After having reached the temperature of 180°C over 10 minutes, the modifier was added and the mixing was continued for three hours.
• Specimens employed for characterization tests have been prepared immediately after the end of the mixing and were stored at room temperature or in refrigerator.
• Ethylene-propylene copolymers containing from about 50 to about 60% by weight of ethylene and having intrinsic viscosity 1.6, 1.8 and 2.4 dl/g have been prepared according to the above described process (Copolymers A, B and C, see Table 1).
• Copolymers have been mixed with SR and VB bitumens according to the above described method.
• the characteristics of the bituminous composition obtained from Copolymers A and C are reported in Table 4.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Civil Engineering (AREA)
• Materials Engineering (AREA)
• Structural Engineering (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Road Paving Structures (AREA)

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